CN104566405A - PTA (purified terephthalio acid) oxidized tail gas catalytic combustion processing method with low energy consumption - Google Patents
PTA (purified terephthalio acid) oxidized tail gas catalytic combustion processing method with low energy consumption Download PDFInfo
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- CN104566405A CN104566405A CN201410731419.4A CN201410731419A CN104566405A CN 104566405 A CN104566405 A CN 104566405A CN 201410731419 A CN201410731419 A CN 201410731419A CN 104566405 A CN104566405 A CN 104566405A
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention discloses a PTA (purified terephthalio acid) oxidized tail gas catalytic combustion processing method with low energy consumption. Oxidized tail gas from a high-pressure absorbing tower enters a catalytic combustion pre-heater and is heated to 295-300 DEG C, and then is mixed fully with assistant fuel methanol and fed into a combustion reactor, wherein the addition of methanol is 6.5-7.0kg/t PTA, the operation pressure of the catalyst combustor is 1.0-1.2MPa, the gas inlet temperature is 295-300 DEG C, and the normal outlet temperature is 395-405 DEG C. Through catalytic combustion reaction, a small amount of organic matter and CO in the oxidized tail gas is combusted to generate CO2 and H2O, and methyl bromide is converted to bromide and hydrogen bromide. Most part of gas from the catalyst combustor enters into a tail gas expanding machine to act to recover energy. The gas inlet temperature of the tail gas expanding machine is 395-405 DEG C, the inlet pressure is 1.0-1.2MPa, the gas outlet temperature is 105-115 DEG C and the outlet pressure is 0.1MPa. The tail gas outputted from the expanding machine is washed with alkali by a tail gas washing tower to remove HBr and Br2, and then is exhausted into air after reaching an environmental protection emission standard. Compared with an existing HPCCU technology, the mechanical consumption amount is reduced by 6.5-7.0kg/tPTA, the methanol consumption amount is reduced by about 50%, the energy consumption of the catalytic combustion system is reduced significantly, the processed tail gas reaches the environment emission standard, and the economic benefits are significant.
Description
Technical field
The present invention relates to a kind of PTA oxidized tail gas catalytic combustion processing method of low energy consumption, this tail gas comes from the oxidation section of p-phthalic acid (PTA) process units, belongs to chemical production technology technical field.
Background technology
P-phthalic acid's (Purified Terephthalio Acid is called for short PTA) is the raw material producing polyester, mainly for the production of PETP (being called for short PET).PTA mainly adopts paraxylene (P-Xylene is called for short PX) air oxidation process to produce at present, and typical production technology is made up of PX oxidation unit and TA hydrofinishing unit two parts.Raw material paraxylene (PX) is dissolved in acetic acid-aqueous solvent, with cobalt acetate/manganese acetate/hydrogen bromide for catalyst, oxidation reaction is there is in the oxygen in PX and air in oxidation reactor, reaction temperature 191-201 DEG C, pressure 1.25-1.65 MPa, generates terephthalic acid (TPA) (TA); Oxidation liquid, again through crystallization, filtration, drying, obtains crude product TA.Crude terephthalic acid (TA) obtains PTA product after hydrofinishing imurity-removal.
Give vent to anger containing a certain amount of acetic acid (HAc), water (H in the top of PX oxidation reactor
2and nitrogen (N O)
2), oxygen (O
2), accessory substance carbon dioxide (CO
2), carbon monoxide (CO), and a small amount of organic matter paraxylene (PX), Methyl acetate (MA), Celfume (CH
3br) etc.This admixture of gas is introduced into cooler and carries out gas-liquid separation, and partial condensation liquid is back to reactor, and a part of condensate liquid goes dehydrating tower to carry out being separated of acetic acid and water, and the uncooled gas got off is PTA oxidized tail gas.
In more newly-built PTA process units (PX oxidizing reaction temperature 193-200 DEG C, pressure 1.35-1.65 MPa) in recent years, high-pressure catalytic combustion method be have employed to the process of PTA oxidized tail gas.The tail gas of PX oxidation reaction, first through high pressure absorber washing, reclaims paraxylene and methyl acetate, then after gas-liquid separation, enters high-pressure catalytic combustion system (HPCCU).Enter in HPCCU oxidized tail gas before treatment containing a large amount of N
2, a small amount of O
2, CO
2, H
2the CO (Approximately 0.5 wt % of O and minute quantity), organic matter (< 0.2 wt %).Oxidized tail gas from high pressure absorber is sent in heater exhaust gas, by Steam Heating to about 300 DEG C, enters catalytic combustion reactor after then fully mixing with auxiliary fuel methyl alcohol, pressure 1.05 ~ 1.25 MPa; Along with gas flow is through catalyst, organic matter (VOC), CO burning generates CO
2and H
2o, Celfume is converted into bromine and hydrogen bromide.The temperature of catalytic combustion reactor exit gas about 450 DEG C, pressure 1.05 ~ 1.25 MPa.Enter off-gas expander from catalytic burner most gases out to recover energy, from decompressor tail gas out through tail gas washing tower alkali cleaning, removing HBr and Br
2after, reach environmental emission standard, by smoke stack emission to air.
The former setting of existing high-pressure catalytic combustion system (HPCCU) technology and adopt process conditions be: (1) catalytic burner operating pressure 1.05 ~ 1.25 MPa, gas inlet temperature about 300 DEG C, normal exit temperature is 450 ~ 455 DEG C; (2) for ensureing that catalytic combustion temperature reaches 450 DEG C, a certain amount of auxiliary fuel methyl alcohol need be added, methyl alcohol addition 13 ~ 14 kg/tPTA.(3) gas inlet temperature 450 ~ 455 DEG C of off-gas expander, pressure 1.05 ~ 1.25 MPa, gas outlet temperature 135 ~ 140 DEG C, pressure 0.1 MPa.This high-pressure catalytic combustion system can remove organic matter and CO in oxidized tail gas effectively, cleaning of off-gas, and high-temperature tail gas is promoted the work done of tail gas swollen face machine, recovers energy.But this catalytic combustion process Shortcomings part: is that energy consumption is higher, needs to consume more fuel methanol, about needs 13.5kg/tPTA.Two is off-gas expander inlet temperature higher (450 DEG C), and decompressor runs at high temperature 450 DEG C, requires high to decompressor material, and the air-flow wave resistance that off-gas expander runs into when high temperature does work is large, and when recovering energy, loss is larger.
In order to overcome the technical shortcoming of existing HPCCU, high-pressure catalytic combustion system process conditions must be improved.The invention provides
a kind of PTA oxidized tail gas catalytic combustion processing method of low energy consumption, both can reduce catalyst combustion reaction energy consumption, can effectively remove nuisance in oxidized tail gas again, ensure that the tail gas after process reached environmental protection standard discharge.
Summary of the invention
The object of the invention is, for the technical deficiency of the existing HPCCU of PTA process units, to provide
a kind of PTA oxidized tail gas catalytic combustion processing method of low energy consumption, both can reduce catalyst combustion reaction energy consumption, and reduce the inlet temperature of off-gas expander, effectively can remove again CO and a small amount of organic matter (CH in oxidized tail gas
3br, HAC, MA, PX), ensure that the tail gas after process reaches environmental protection standard discharge.
The object of the invention is by following
technical schemerealize:
a kind of PTA oxidized tail gas catalytic combustion processing method of low energy consumption, comprise the following steps:
(1) oxidized tail gas from high pressure absorber enters catalytic combustion preheater, and the first preheater low-pressure steam is heated 130 DEG C, and the second preheater high steam is heated 295 ~ 300 DEG C.
(2) preheated tail gas enters supplementary fuel injection device, fully mixes with auxiliary fuel methyl alcohol, methyl alcohol addition: 6.5 ~ 7.0 kg/tPTA.
(3) enter catalytic combustion reactor from supplementary fuel injection device tail gas out, carry out catalyst combustion reaction, organic matter (VOC), CO burning generates CO
2and H
2o, Celfume is converted into bromine and hydrogen bromide.
The operating condition of catalytic burner is: operating pressure 1.0 ~ 1.2 MPa, gas inlet temperature 295 ~ 300 DEG C, and normal exit temperature is 395 ~ 405 DEG C; Gas normal discharge 2400 ~ 2670 kg/tPTA.
(4) from catalytic burner most gas (Approximately 90wt% out) enter off-gas expander acting and recover energy.(small portion of gas send and the use of inertia protection gas as wind after entering the process of tail gas drying system.)
The operating condition of off-gas expander is: gas inlet temperature 395 ~ 405 DEG C, inlet pressure 1.0 ~ 1.2MPa; Gas outlet temperature 105 ~ 115 DEG C, outlet pressure 0.1 MPa.
(5) tail gas washing tower is entered from off-gas expander tail gas out, with 4.5 ~ 6 wt % alkali liquid washings, removing HBr and Br wherein
2, the tail gas after purification reaches environmental emission standard, by smoke stack emission in air.
Further illustrate, PTA oxidized tail gas of the present invention comes from the oxidation section of PTA device, and the operating condition of PTA device PX oxidation reactor is: reaction temperature 193-200 DEG C, pressure 1.35-1.65 MPa.Oxidized tail gas is first through high pressure absorber washing, and reclaim paraxylene and methyl acetate, after gas-liquid separation, tail gas enters high-pressure catalytic combustion system (HPCCU).
Further illustrate, in described step (3), tail gas catalyzed combustion reaction employing catalyst is:
Pt/Pd catalyst, catalyst space velocities: 550 ~ 610h
-1; Catalyst keeps active normal running temperature scope: 290 ~ 460 DEG C.
Compared with existing HPCCU technology, of the present invention
beneficial effectbe:
(1) auxiliary fuel methyl alcohol addition changes into 6.5 ~ 7.0kg/tPTA by original setting value 13.0 ~ 14.0kg/tPTA;
Keep catalytic burner operating pressure constant, catalytic burner normal exit temperature changes into 400 ~ 405 DEG C by original setting value 450 ~ 455 DEG C.This process modification makes methanol consumption amount reduce by 6.5 ~ 7.0kg/tPTA, and methyl alcohol consumption declines about 50%, and catalytic combustion system energy consumption declines obviously, can reduce the processing cost of tail gas, remarkable in economical benefits.
(2) keep off-gas expander inlet pressure constant, expander inlet temperature changes into 400 ~ 405 DEG C by original setting value 450 ~ 455 DEG C, and off-gas expander outlet changes into 105 ~ 115 DEG C, 0.1 MPa by original setting value 135 ~ 140 DEG C, 0.1 MPa.And off-gas expander outlet does not have aqueous water to generate, reducing outlet temperature can not cause corrosion to decompressor.This process modification off-gas expander service condition is slowed down and, mechanical efficiency becomes large.
(3) catalyst combustion reaction is at 1.0 ~ 1.2 MPa, 295 ~ 405 DEG C of range of operation, can ensure that the oxidized tail gas after purified treatment reaches environmental protection standard discharge.
Accompanying drawing explanation
Fig. 1 is high-pressure catalytic combustion system process chart.
In figure: 1-first preheater, 2-second preheater, 3-supplementary fuel injection device, 4-catalytic burner, 5-off-gas expander, 6-tail gas washing tower.
Detailed description of the invention
Below in conjunction with instantiation, the invention will be further described, but embodiments of the present invention are not limited thereto.
embodiment 1
Certain PTA plant capacity 600 kt/a, the operating condition of PX oxidation reactor is reaction temperature 194-200 DEG C, pressure 1.4-1.6 MPa.Oxidized tail gas washs through high pressure absorber, and reclaim paraxylene and methyl acetate, after gas-liquid separation, tail gas enters high-pressure catalytic combustion system (HPCCU).Catalytic combustion oxidized tail gas before treatment composition (wt %) is as follows:
N
2(92.85%), O
2(3.98%), CO
2(2.16%), H
2o (0.37%), CO (0.51 %), CH
3br (0.0077 %), all the other organic matters (0.1 %); Oxidized tail gas flow 2639 kg/tPTA.
Catalytic combustion process concrete steps after improvement are as follows:
(1) oxidized tail gas from high pressure absorber enters catalytic combustion preheater, and the first preheater low-pressure steam is heated 130 DEG C, and the second preheater high steam is heated 300 DEG C.
(2) preheated tail gas enters supplementary fuel injection device, fully mixes with auxiliary fuel methyl alcohol, methyl alcohol addition 7.0 kg/tPTA,
(3) enter catalytic combustion reactor from supplementary fuel injection device tail gas out, carry out catalyst combustion reaction, organic matter (VOC), CO burning generates CO
2and H
2o, Celfume is converted into bromine and hydrogen bromide.
The operating condition of catalytic burner is: operating pressure 1.12 MPa, gas inlet temperature 300 DEG C, and normal exit temperature is 405 DEG C; Catalyst space velocities 590h
-1.
(4) from catalytic burner most gas (Approximately 90wt% out) enter off-gas expander acting and recover energy.(small portion of gas enters the process of tail gas drying system.)
The operating condition of off-gas expander is: gas inlet temperature 405 DEG C, inlet pressure 1.12MPa; Gas outlet temperature 115 DEG C, outlet pressure 0.1 MPa.
(5) tail gas washing tower is entered from off-gas expander tail gas out, with 4.9 wt % NaOH solution washings, removing HBr and Br wherein
2, the tail gas after purified treatment reaches environmental emission standard, by smoke stack emission in air.
After catalytic combustion process, tail gas composition (wt %) of (expander inlet) is as shown in table 1:
table 1 embodiment 1tail gas composition before and after catalytic combustion process
Methyl alcohol addition 7.0 kg/tPTA, catalyst combustion reaction is at 1.12 MPa, and 300 ~ 405 DEG C of range of operation, can ensure that in tail gas, CO conversion ratio is greater than 98%, conversion rate of organic matter is greater than 98%, and Celfume conversion ratio is greater than 90%.Environmental administration is to the display of tail gas washing tower Waste gas outlet sampling inspection results, and the oxidized tail gas after catalytic combustion process reaches environmental emission standard completely, in table 3.PTA plant running three months, to the display of off-gas expander corrosion condition testing result, off-gas expander ruuning situation is normal, in table 4.
embodiment 2
Certain PTA plant capacity 600 kt/a, the operating condition of PX oxidation reactor is reaction temperature 194-200 DEG C, pressure 1.4-1.6 MPa.Oxidized tail gas washs through high pressure absorber, and reclaim paraxylene and methyl acetate, after gas-liquid separation, tail gas enters high-pressure catalytic combustion system (HPCCU).Catalytic combustion oxidized tail gas before treatment composition (wt %) is as follows:
N
2(92.9%), O
2(3.96%), CO
2(2.15%), H
2o (0.37%), CO (0.51 %), CH
3br (0.0078 %), all the other organic matters (0.1 %); Oxidized tail gas flow 2598 kg/tPTA.
Catalytic combustion process concrete steps after improvement are as follows:
(1) oxidized tail gas from high pressure absorber enters catalytic combustion preheater, and the first preheater low-pressure steam is heated 130 DEG C, and the second preheater high steam is heated 295 DEG C.
(2) preheated tail gas enters supplementary fuel injection device, fully mixes with auxiliary fuel methyl alcohol, methyl alcohol addition 6.5 kg/tPTA,
(3) enter catalytic combustion reactor from supplementary fuel injection device tail gas out, carry out catalyst combustion reaction, organic matter (VOC), CO burning generates CO
2and H
2o, Celfume is converted into bromine and hydrogen bromide.
The operating condition of catalytic burner is: operating pressure 1.12 MPa, gas inlet temperature 295 DEG C, and normal exit temperature is 400 DEG C; Catalyst space velocities 580h
-1.
(4) from catalytic burner most gas (Approximately 90wt% out) enter off-gas expander acting and recover energy.(small portion of gas enters the process of tail gas drying system.)
The operating condition of off-gas expander is: gas inlet temperature 400 DEG C, inlet pressure 1.12MPa; Gas outlet temperature 110 DEG C, outlet pressure 0.1 MPa.
(5) tail gas washing tower is entered from off-gas expander tail gas out, with 4.8 wt % NaOH solution washings, removing HBr and Br wherein
2, the tail gas after purified treatment reaches environmental emission standard, by smoke stack emission in air.
After catalytic combustion process, tail gas composition (wt %) of (expander inlet) is as shown in table 2:
table 2 embodiment 2tail gas composition before and after catalytic combustion process
Methyl alcohol addition 6.5kg/tPTA, catalyst combustion reaction is at 1.12 MPa, and 295 ~ 400 DEG C of range of operation, can ensure that in tail gas, CO conversion ratio is greater than 98%, conversion rate of organic matter is greater than 98%, and Celfume conversion ratio is greater than 90%.Environmental administration is to the display of tail gas washing tower Waste gas outlet sampling inspection results, and the oxidized tail gas after catalytic combustion process reaches environmental emission standard completely, in table 3.PTA plant running three months, to the display of off-gas expander corrosion condition testing result, off-gas expander ruuning situation is normal, in table 4.
table 3tail gas washing tower Waste gas outlet sampling inspection results
table 4off-gas expander corrosion condition testing result
Claims (3)
1. a PTA oxidized tail gas catalytic combustion processing method for low energy consumption, is characterized in that, comprise the following steps:
(1) oxidized tail gas from high pressure absorber enters catalytic combustion preheater, and the first preheater low-pressure steam is heated 130 DEG C, and the second preheater high steam is heated 295 ~ 300 DEG C;
(2) preheated tail gas enters supplementary fuel injection device, fully mixes with auxiliary fuel methyl alcohol, methyl alcohol addition: 6.5 ~ 7.0 kg/tPTA;
(3) enter catalytic combustion reactor from supplementary fuel injection device tail gas out, carry out catalyst combustion reaction, organic matter (VOC), CO burning generates CO
2and H
2o, Celfume is converted into bromine and hydrogen bromide; The operating condition of catalytic burner is: operating pressure 1.0 ~ 1.2 MPa, gas inlet temperature 295 ~ 300 DEG C, and normal exit temperature is 395 ~ 405 DEG C; Gas normal discharge 2400 ~ 2670 kg/tPTA;
(4) from catalytic burner most gas (Approximately 90wt% out) enter off-gas expander acting and recover energy, the operating condition of off-gas expander is: gas inlet temperature 395 ~ 405 DEG C, inlet pressure 1.0 ~ 1.2MPa; Gas outlet temperature 105 ~ 115 DEG C, outlet pressure 0.1 MPa;
(5) tail gas washing tower is entered from off-gas expander tail gas out, with 4.5 ~ 6 wt % alkali liquid washings, removing HBr and Br wherein
2, the tail gas after purification reaches environmental emission standard, by smoke stack emission in air.
2. the PTA oxidized tail gas catalytic combustion processing method of a kind of low energy consumption according to claim 1, is characterized in that,
Described PTA oxidized tail gas comes from the oxidation section of PTA device, the operating condition of PTA device PX oxidation reactor is: reaction temperature 193-200 DEG C, pressure 1.35-1.65 MPa, oxidized tail gas first washs through high pressure absorber, reclaim paraxylene and methyl acetate, after gas-liquid separation, oxidized tail gas enters high-pressure catalytic combustion system.
3. the PTA oxidized tail gas catalytic combustion processing method of a kind of low energy consumption according to claim 1, is characterized in that, in described step (3), tail gas catalyzed combustion reaction employing catalyst is: Pt/Pd catalyst, catalyst space velocities: 550 ~ 610h
-1; Catalyst keeps active normal running temperature scope: 290 ~ 460 DEG C.
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| CN108854444A (en) * | 2018-05-15 | 2018-11-23 | 安徽亿普特集团有限公司 | A kind of exhaust gas comprehensive processing technique |
| CN114180520A (en) * | 2021-12-09 | 2022-03-15 | 四川天采科技有限责任公司 | Coproduction process for catalytic oxidation of PTA hydrogen extraction tail gas and hydrogen production from methanol |
| CN115849407A (en) * | 2022-12-13 | 2023-03-28 | 上海泓济环保科技股份有限公司 | Method for removing organic matters in waste salt by oxygen-enriched gasification coupled catalytic combustion |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 625 Applicant after: Nanjing Scientific Professional School Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 625 Applicant before: Nanjing College of Chemical Technology |
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